5-chlorothioimino imidazolidines

ABSTRACT

5-Chlorothioimino imidazolidines are produced by the reaction of sulfur dichloride and a 5-imino imidazolidine in the presence of a rate determining amount of an acid acceptor. The 5chlorothioimino imidazolidines are useful intermediates in the preparation of pesticides.

United States Patent [191 [1 1/ 3,843,677 Cleveland Oct. 22, 1974 S-CHLOROTHIOIMINO IMIDAZOLIDINES 3.699.122 10/1972 Kohn 260/56] s [75] Inventor: James D. Cleveland, Albany, Calif. FOREIGN PATENTS OR APPLICATIONS Assignee: Chevron Research Company San France Francisco, Calif. P E N T f rimary xaminer ata le rouso [22] Flled: May 1972 Attorney, Agent, or Firm-G. F. Madgeburger; John [21] Appl. NO; 251,479 Stoner, .lr.; Raymond Owyang 52 US. Cl..... 260/3095, 71/92 [57] FE [51] Int. Cl C07d 49/32 5-Chl9r9lhi01min9 lmldalolldmes are producred y the 58 Field of Search 260/3095, 309.7 reaction of Sulfur dichloride and a 5-imin9 imidazolidine in the presence of a rate determining amount of [56] References Cit d an acid acceptor. The S-chlorothioimino imidazoli- UNn-ED STATES PATENTS dines are useful intermediates in the preparation of 3,663,594 5/l972 Brown et al 260/479 C pesncldes' 3.679.733 7/l972 Brown 260/479 C 4 Claims, No Drawings 1 -cHLo oTH1or rNo IMIDAZQLIDINES FIELD OFTHE INVENTION This invention relates to a process for producing sulfenyl chloride Nchlorothioimino) derivatives of imino substituted imidazolidines Processes for producing sulfenyl chloride derivatives of compounds having active hydrogenatoms substituted on nitrogen are known. E. Kuhle, Synthesis, 561 1970), discloses the preparation of'sulfenyl halide derivatives of sulfoamides and "amines; U.S. 'Ser'. No. 45,902 of G. KvKohn, filed June 12,1970, nowU.S. Pat. No. 3,699,122, discloses the preparation of-sulfenyl halide derivative of amides. U .S. Ser. Nos. 88,105 and 88,212 of M. S. Brown and G. K. Kohn, filed Nov. 9, 1970, now US. Pat. Nos. 3,679,733 and 3,755,437 respectively, disclose the preparation of sulfenyl halide derivatives of urea and carbama'te compounds-.

DESCRIPTION OF THE INVENTION d The novel compounds of'this invention can be represented by the formula 0 to 6 halogens of atomic number 9 to 35 (fluorine, chlorinevor bromine cycloalkyl of 3 to carbon dibromoethyl,

. v l 2 l ,l,2,2-tetrachloroethyl, trichloromethyl, 2,2- 1,1 ,Z-trichloroethyl, 2,2,2- trichloroethyl, 2,4-dichloropropy'l, 2,6-difluorohexyl; and halocycloalkyl' such as 2-chlorocyclopentyl, 4- bromocyclohexyl, and 2-methyl-3-chlor0cyclohexyl.

Representative hydrocarbyl aryl groups which R and R may represent include phenyl; naphthyl; alkaryl of 7 to 10 carbon atoms such as 2-methylphenyl, 3- methylphenyl, 4-ethylphenyl, 2,4-dimethylphenyl, 3- sec-butylphenyl'; and aralkyl of 7 .to 10 carbon atoms such as benzyl, 3-phenylpropyl, and 4-phenylbutyl.

Representative substituted aryl groups which R and I R may represent include halo-substituted aryl groups such 2-fluorophenyl, chlorophenyl, 3-chlorophenyl, 4-trifluoromethylphenyl,

4-fluorophenyl, 2-

3,4-dichlorophenyl, 3-chloro-4-bromophenyl,

2 chloro-4-methylphenyl, 2-fluoro-4-methylphenyl, 4-

atoms substituted with 0m 6 halogens of atomic numher 9 to 35or aryl of 6 to .12 carbon atoms substituted with O to 5 halogens; of atomic number 9 to 35, nitro groups, alkoxy groups individually of l to 4 carbon atoms, or trihalomethyl wherein the halogen is fluorine alko'xy-substituted aryl groups such as 4- methoxyphenyl, 4'-ethoxyphen.yl, 4-methoxy-2- methylphenyl,4-methoxybenzyl; nitro-substituted aryl groups such as Z-nitrophenyl; 4-nitrophenyl and 4- nitrobenzyl; and aryl groups substituted with different substituents such as 2-methoxy-4- chlorophenyl and 2- chloro-4-nitrophenyl. Substituted aryl groups-preferaor chlorine. Preferably: either R orR will be alkyl or cycloalkyl, optionallysubstituted as the casemayzbe,

and the other 'of R or R will be tuted as the case may. be. .3

R is alkyl of l to 6 carbon atoms and R -is phenyl substituted with 0 to 3 halogens ofatomic number 9 to 35 i.e., phenyl and phenyl substituted Withl to 3 halogens of atomic number 9 to '35 or alkphenyl of 7 to aryl, optionally substi- 7 10 carbon atoms substituted with 0' to 3 halogens of atomic number 9 to 35 i.e., alkphenyl of 7 to-10 carbon atoms and alkphenyl of 7 to 10 carbon atoms sub stituted with 1 to 3 halogens of atomic number 9 to 35 'Altematively, either R orR is alkyl of '.l to 4'carbori atoms and the other of R" or R' is phenyl substituted with 0 to 3 halogens of atomic number 9 to 35 or alkaryl of 7 to 10 carbon atoms substituted with 0 to 3 haloimidazolidinedione, l-trichloromethyl-3-l 3-chloro-4- bromo'phenyl)-5-chlorothioimino-2,4- imidazolidinedione, l-phe nyl-3 1,2,2,2- tetrachloroethyl)-5chlorothioimino-2,4- imidazolidinedione, ,1-cyclohexyl-3-(4- methoxyphenyl)-5-chlorothioimino-2,4- imidazolidinedione, l-('4-chlorocyclohexyl)-3-( 4- nitrophenyl)-5-chlorothioimino-2,4-

iinidazolidinedione, v l-phenyl-3-(4- trifluoromethylphenyl)-5-chlorothi oimino-2,4

imidazolidinedione, l-methyl-3-methyl-5- chlorothioimino-Z,4-imidazolidinedione, l-benzyl-3- rnethyl-S-chlorothioimino-Z,4-imidazolidinedione, l-nbutyl-3-l 3-phenylpropyl)-5-chlorothioimino-2,4-

gens of atomic number 9 to 35 lnanotheraltemative,

phenyl substituted with one halogen of atomicnumber 9 to 35.

Representative, aliphatic and cycloaliphatie groups chloromethyl, bromomethyl, fluoromethyl, dichlo'romethyl, trifluoromethyl, l,2,2,2,-tetrachloroethyl,,

R is alkyl of l to 4 carbon atoms and R is phenyl or imidazolidinedione, and

chlorothioimino-2,4-imidazolidinedione.

Representative, 5-chlorothioimino-imidazolidine- 2-one-4-thionesl wherein Y is sulfur) include l-methyl- 3-( Z-fluorophenyl)-5-chlorothioimino-imidazolidine- 2-one-4-thione, lmethyl-3-methyl-5-chlorothioiminoimidazolidine-2-one-4-thione, 1-cyclohexyl-3-phenyl- 5 -chl0rothioimino-imidazolidine 2-one-4-thione, l-( 2- fluorophenyl)-3 -trichlorornethyl-5-chloroethioiminoimidazolidine-2-one-4 thione, l-f 3-chlorocyclohexyl)- 3-( 2-nitrophenyl )5-chlorothioimino-imidazolidine- V l-( 3-methoxyphenyl)-3-( 2- methylphenyl)-5-chlorothioimino-imidazolidine- 2'-one-4 -thione, l-(4-chlorobenzyl)-3-(2- methylphenyl)-5-chlorothioimino-imidazolidine- 2-one-4-thione, and l-propyl-3 -(a-naphthyl) chlorothioimino-imidazolidine-2-one-4-thione.

Representative 5-chlorothioin1ino-2-imidazolidinone (wherein Y represents 'two hydrogens) include 1- methyl-3-( 2- fluorophen yl)-5-chloroimino-2- imidazoli'dinone, ,lmethyl-3-( 3,4-dichlorophenyl)-5- chloroiminoQ-imidazolidinone, l-( 2-fluorophenyl)-3- a-napthyl) 3.-methyl-5-chloroimino-2- imidazolidinone. r

The S-chlorothioimino imidazolidines are prepared in accordance with the following reaction ('1):

wherein R, R and Y have the same significance as previously defined and B is an acid acceptor.

- The acid acceptor is an organic base such as pyridine compound or a trialkylamine compound. Suitable pyridine compounds are pyridine and pyridine compounds of 6 to 10 carbon atoms and of l to 2 alkyl groups such as 2-methylpyridine, 2-ethylpyridine, 3- methylpyridine, 3,5'-dimethylpyridine, and 2- butylpyridine. Suitable trialkyamine's are those wherein the. alkyl group contains individually l to 4 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine.

The sulfur dichloride and .the imidazolidine compound are employed in substantially equimolar amounts, e.g., the molar ratio of sulfur dichloride to the imidazolidine compound generallyvaries from about l.5:l to 1:1.5, although molar ratios of sulfur dichloride to the imidazolidine compound of 14:1 to l.l:1 are preferred. The molar ratios of acid acceptor to sulfur dichloride is also substantially equimolar, e.g., the molar ratio of acid acceptor to sulfur dichloride varies moles of the reactant and the 5-chlorothioimino from about 1.211 to 1:12, although molar ratios of acid acceptor to sulfur dichloride of 1:1 to 1:12 are preferred.

In'order to produce the 5-chlorothioimino imidazolidine compounds of the invention in high yield, it is essential to react the imidazolidine and sulfur dichloride in the presence of a limited amount of free, uncomplexed (unreacted) acid acceptor. This is suitably accomplished by the addition of the acid'acceptor to a substantially equimolar mixture of the imidazolidine and the sulfur dichloride so that the moles of free acid acceptor to the total moles of imidazolidine reactant and 5- chlorothioimino imidazolidine product is less than 0.2: 1., preferably less than 0.1 :1, and more preferably less than 0.05: l. In other words, during the course of the reaction between the sulfur dichloride and the imidazolidine reactants, there should be at least 5 imidazolidine product per mole of acid acceptor which is not complexed with hydrochloric acid. Provided that the reaction is conducted with the restricted amount of acid acceptor indicated above, the contacting of the acid acceptor with the mixture of the imidazolidine and the sulfur dichloride can be conducted by a variety of procedures. In one modification, the acid acceptor is added in increments, e. g., dropwise, in an'inert diluent, if desired, to a mixture of the imidazolidine and sulfur dichloride in an inert diluent. In another modification, the acid acceptor is addedcontinuously to a mixture of the imidazolidine and sulfur dichloride in an inert diluent.

Suitable inert diluents for the reaction include alkanes of 5 to 10 carbon atoms, such as hexane, isooctane and decane; aromatic compounds such as benzene and chlorobenzene; oxygenated hydrocarbons such as acyclic alkyl ethers, e.g., dimethoxyethane and dibutyl ethers; and cycloalkyl ethers, e.g., dioxane, tetrahydrofuran and tetrahydropyran. Other suitable diluents include nitriles such as acetonitrile and propionitrile; d-ialkylamides such as dimethylformamide, and dialkylsulfoxides such as dimethylsulfoxide. Preferred diluents are chlorinated hydrocarbons of 1 to 2 carbon atoms, such as methylene dichloride, chloroform, carbon tetrachloride and ethylene dichloride. Generally, the amount of diluent employed ranges from 1 to 50 moles per mole of sulfur dichloride. The reaction is suitable conducted at a temperature between 20C. and the boiling point of the diluent, although temperatures between 0C. and 50C. are preferred. The reaction is conducted at or above atmospheric pressure.

In addition to the imidazolidine reactants represented by formula II, the process of the invention is broadly applicable for the preparation of chlorothi- .oimino derivatives of any compound containing an imino substituent, i.e., a -C=N--H group.

UTILITY EXAMPLE 1 l-( 2-fluorophenyl)-3-methyl-5-chlorothiomino imidazolidinedione A 3.7 g (0.048 mole) sample of pyridine was added dropwise to a slurry of 8.84 g (0.04 mole) l-(2- fluorophenyl)-3-methyl-5-imino-2,4-

imidazolidinedione and 4.53 g (0.044 mole) sulfur di- I chloride in 40 ml of methylene dichloride. At the end stirred at about 25C. for 30 minutes and filtered to give a solution of the S-chlorothi'oimino product in. methylene dichloride.

EXAMPLE 2 l-( Z-fluorophenyl )-3-methyl-S-phenyldithioimino-Z,4- imidazolidinedione A solution of about 0.04 mole of 1-(2-f1uorophenyl)- 3-methyl-5-chlorothioimino 2,4-imidazolidinedione in 40 ml of methylene-dichloride was prepared as described in' Example 1.

To this solution (cooled to 0C.) was added dropwise a solutionof 3.96 g (0.036 mole) phenyl mercaptan and '3. 1 6 g (0.04 mole) pyridine. The resulting reaction mixture was stirred at about 0C. for. 10 minutes,

washed with water, washed with sodium bicarbonate solutiomdried over magnesium sulfate andevaporated under reduced pressure to give'a yellow solid residue.

The residuewas taken up in benzene and filtered. The filtrate was chromatographed on silica (benzene elution) to give the imidazolidinedione product as ayellow solid. The product was recrystallized from chloroform/ether to give a light yellow solid, m.p.

89.590.5C. Elemental analysis showed:

Calc. Found EXAMPLE 3 evaporated under reduced pressure to give a yellowish white residue. The residue was slurried with ethanol and filtered. The filtrate was evaporated to give the product m.p. 78-85C. Elemental analysis showed:

EXAMPLE 4 1-( 2-fluorophenyl )-3-methyl-5- carbethoxymethyldithioimino-2,4-imidazolidinedione A solution of 10.8 g (0.09 mole) ethyl 2- mercaptoacetate and 7.9 g 0.1 mole) pyridine in 20 ml of methylene chloride was added dropwise to a solution of about 0.09 mole of 1-( Z-fluorophenyl)-3-methyl-5- chlorothioimino-2,4-imidazolidinedione in 135 ml methylene chloride at 0C. The resulting reaction mixture was stirred for about 30 minutes at 0C., washed with water, washed with sodium bicarbonate, dried over magnesium sulfate and evaporated under reduced pressure to give a yellow solid residue. The residue was taken up in benzene and filtered. The filtrate was di luted with hexane and cooled to 0C. to crystallize out 15 g of the product as a pale yellow solid, m.p. 79-8'2C. Elemental analysis showed: 1

Calc. Found s I 17.3 16.6 F 5.1 5.3'

. 7 EXAMPLE 5 1-( 2-fluorophenyl)-3-methyl-5-methoxythioimino-2,4- I

imidazolidinedione A solution of 3.2 g (0.1 mole) methanol and 7.9 g 0.1 mole) pyridine in 20 ml of methylene chloride was added dropwise to a solution of about 0.1 mole of 1-( 2- fluorophenyl)-3-methyl-5-chlorothioimino-2,4- imidazolidinedione in 100 ml of methylene chloride at 0C. The resulting reaction mixture was stirred for about 30 minutes at 0C., washed with water, washed with sodium bicarbonate, dried over magnesium sulfate, and evaporated under reduced pressure to give a yellow solid residue. The solid was washed with isopropyl alcohol to give the product as a pale yellow solid, m.p. 124l27C. Elemental analysis showed:

Calc. Found Calc. Found C 47.7 48.8 S 11.3 11.4 H 4.3 4.0 F 6.7 6.5 N 12.8 13.1 5 s 19.6 18.5 5

EXAMPLE 6 By a similar procedure, 1-( 2-fluorophenyl)-3-methyl- 5-chlorothjoimino-2 ,4-imidazolidinedione was reacted with methyl mercaptan and n-butyl mercaptan to give, respectively, 1-( 2-fluorophenyl)-3-methyl-5- methyldithioimino-2,4-imidazolidinedione [RE-1768 1 m.p. l30-133C.; C% 45.2; 11%, 2.9; N%, 13.9 and 8%, n and 1-(2-fluorophenyl)-3:methyl-5 nbutyldithioimino-2,4-imidazolidinedione [RE-17682 m.p. 77-80C.; C%, 50.6; 11%, 4.4; N%, 12.6 and 8%, 17.4].

Herbicide Tests Pi'eand post-emergence herbicidal tests on the Seeds of the test vegetation were planted in a pot of soil and the imidazolidine solution was sprayed uniformly onto the soil surface at a dose of 100 micro- A to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.

The results of these tests appear in Table I.

Table l COMPOUND Herbicidal Effectiveness Pre/Post W C M P L lOO/O l00/l0 l00/l0 l00/l00 l00/l00 [00/100 100/20 100/2 0 l00/l00 l00/l00 100/I00 100/l0 100/0 l000/l00 l00/l00 100/X00 100/l0 100/0 100/100 100/90 l00/l00 100/0 l00/0 l00/l00 100/I00 l00/l00 l00/30 v 100/l5 100/[00 100/80 100/90 0 Wild Oats W Wate'rgrass C Crabgrass M Mustard P Pigweed L Lambsquarter (Avena fatua) grams per cm The pot waswatered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerg-. ing seedlings, etc. for a 3-week period. At the end of this period the herbicidaleffectiveness of the imidazolidine was rated based on the physiological observations.

At 0 to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill. Post-Emergence Test The test imidazolidine was formulated in the same manner as described above for the pre-emergence test. The concentration of the imidazolidine in this formulation was 5,000 ppm. This formulation was uniformly sprayed on 2 replicate pots of 24-day-old plants (approximately l to 25 plants per pot) at a dose of 100 micrograms per cm After the plants had dried, they were placed in a greenhouse and then watered intermit tently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses tothe treatment. After 3 weeks the herbicidal effectiveness of the imidazolidinedione was rated based on these observations.

(Echinochloa crusgalli) (Digitaria Sanguinalis) Brassica arvensis) (Amaranthus'retruflexus) qngpodium album) I claim:

40 wherein Y is oxygen or sulfur, R is alkyl of l to 6 carbon atoms, and R is, phenyl, phenyl substituted with 1 to 3 halogens of atomic number 9 to 35, alkphenyl of 7 to 10 carbon atoms or alkphenyl of 7 to 10 carbon atoms substituted with l to 3 halogens of atomic number 9 to 35. 2. The compound of claim 1 wherein Y is oxygen. 3. The-compound of claim 1 wherein Y IS oxygen, R is alkyl of 1 to 4 carbon atoms and R is phenyl or phenyl substituted with l halogen of atomic number 9 to 35.

4. The compound of claim 3 wherein R is methyl and R is 2-fluorophenyl. 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein Y is oxygen.
 3. The compound of claim 1 wherein Y IS oxygen, R1 is alkyl of 1 to 4 carbon atoms and R2 is phenyl or phenyl substituted with 1 halogen of atomic number 9 to
 35. 4. The compound of claim 3 wherein R1 is methyl and R2 is 2-fluorophenyl. 